Dye carrier compositions



United States Patent 3,471,248 DYE CARRIER COMPGSITIONS Alfred Schaeuble, Riehen, Ernst Adolf Rauchle, Basel,

and Willi Lentenegger, Basel-Land, witzerland, assignors to J. R. Geigy A.G., Basel, Switzerland No Drawing. Original application May 13, 1964, Ser. No. 367,235. Divided and this application May 24, 1965, Ser. No. 469,960 Claims priority, application Switzerland, May 3, 1962, 5 312/ 6 Int. Cl. D06p 3/14 U.S. Cl. 8-54 7 Claims ABSTRACT OF THE DISCLOSURE This application is a division of application Ser. No. 367,235, filed May 13, 1964, which application is a continuation-in-part application of application Ser. No. 276,065, filed Apr. 26, 1963, and now abandoned; the latter application being the continuation-in-part of application Ser. No. 214,510, filed Aug. 3, 1962, and now abandoned.

The present invention concerns compositions that are useful in the dyeing of polyamide fibers.

The continuous dyeing of polyamide fibers is known. A known process consists, for example, in impregnating wool with a preferably thickened aqueous solution of acid wool dyestuifs at temperatures under the drawing temperature of these dyestuffs, then drying the impregnated goods, passing them through a hot acid bath to fix the dyestuif (acid shock method) and then rinsing. As this process has considerable disadvantages-e.g. it produces uneven dyeingsit has not attained any practical importance.

As a further development of this process, the addition of carriers to the impregnation liquors has already been suggested. As such, water-soluble condensation products of fatty acids having 8 to 14 carbon atoms or of mixtures of such acids with 2 equivalents of dialkanolamine have proved to lead to the best hitherto attainable results. Such condensation products are known as Kritchevsky bases and are obtained according to the process described in the US. Patent No. 2,089,212.

However, the use of these impregnation liquors has also a number of disadvantages. Above all, such impregnation liquors are not stable, as often after a few hours for no apparent external reason they separate irreversibly into two phases, one poor in auxiliaries and the other containing the main amount of dyestuff and auxiliaries. This phase formation in the impregnation liquor makes level dyeing, particularly of large batches, more difficult.

The tendency to phase formation of impregnation liquors has become the standard of their usefulness. However, practical experience has shown that the impregnation liquors of the known process described only produce useful dyeing when the content of dyestuif, electrolytes and auxiliaries is very carefully calculated. Phase formation is particularly strongly dependent on the salt content of the impregnation liquor. But the inclusion of electrolytes in the liquor is unavoidable if, in the continuous process, for example, carbonized and neutralized wool is used which has not been sufficiently carefully rinsed. Such factors adversely influence the evenness of the dyeings obtained by the known process. Finally, if the dyestuff is fixed by passing the impregnated goods through a hot acid bath, previous drying of the goods saturated with the impregnation liquor has proved to be necessary in order to avoid undesirable bleeding in the acid bath.

It has now been found that, contrary to general opinion, surprisingly suitable impregnation liquors for the continuous dyeing of natural and synthetic polyamide fibers are obtained if auxiliaries are added as carriers to aqueous dyestuff solutions which neither on longer standing nor on alteration of the electrolyte content impart a phase formation tendency within the usual technical margins to these liquors.

In a first process according to the invention, thickened aqueous solutions of acid wool dyestufis and thickening agent are used which, as substantial color transfer agent (carrier), contain a mixture of (a) an active amount of soluble salts of saturated aliphatic monocarboxylic acids having 8 to 14 carbon atoms,

(b) polyglycol ethers which are the condensation products of fatty alcohols or fatty acids having 8 to 14 carbon atoms, with ethylene oxide in such amount that the polyglycol ethers contain 4 to 12'ether groups: optionally, the aforesaid color transfer agent may contain other auxiliaries.

Natural or synthetic polyamide fibers are impregnated with such liquors at temperatures which are below the drawing temperature of these dyestuffs and the dyeing of the fiber materials so treated is completed by a heat treatment in a humid medium (steam), without or combined with the action of acid (acid shock bath) and then rinsing, preferably in cold water.

Whereas additions of non-foaming anion' active dispersing agents from the class of aromatic sulfonic acids or their water-soluble salts, in particular ,B-tetrahydronaphthalene sulfonic acid or a mixture or a-and fi-tetrahydronaphthalene sulfonic acid or of their water soluble salts are necessary to maintain the dye liquor in a monophase state when Kritchevsky bases are used, the present process can be performed, completely unexpectedly, without such additions, thus rendering it simpler and more economical to carry out in practice.

It is a particular advantage of the process according to the invention that uniform dyeings are obtained even when large batches are being dyed and, furthermore, that the hot acid shock bath can be applied directly to the Wet impregnated goods which have only been freed mechanically from excess impregnation liquor, for instance by wringing, but retain a content of the liquor of at least about 40% calculated on the weight of the dry goods, without any drying of the goods between the dye bath and the acid shock bath, and that this can be effected without the occurrence of any permanent bleeding and correspond. ing loss of dyestuff from the dyed fibers, as it occurs when Kritchevsky bases are used and when no intermediate dyeing is applied before the acid shock bath. The drawing temperatures of the dyestuffs used, i.e. the temperature at which 60-70% of the amount dyestuif employed in the dyebath has drawn onto the fiber in one minute, at least 70 C. or higher and preferably to C. In the process according to the invention, the impregnation of the fiber materials with the dyestuff must be performed at a temperature below this drawing temperature and above room temperature (20 C.), preferably in the range of 40 to 70 C., and at a pH of at least 5 and up to 11 and even higher, preferably about 6.5 to 8. At a pH lower than 5, the impregnation liquor loses its homogeneous nature (monophase), with ensuing drawbacks of multiphase impregnation as set forth above.

The process according to the invention is excellently suitable for the continuous dyeing of polyamides, particularly of wool, with a one-phase dyebath of the above-defined pH, depending on the alkali-resistance of the fiber being dyed. In contrast thereto, dyebaths containing a carrier solely soluble salts of saturated aliphatic monocarboxylic acids as defined under (a), supra, can be used for dyeing the same above-described fibers only in a pH range of 6.5 and higher.

The invention thus constitutes an important advance in the art of dyeing nitrogen-containing fibers, and especial- 1y of wool on the one hand because, as is Well-known, wool is most advantageously dyed in a pH range below 6 and as closely to the isoelectric point of wool as possible. Thanks to the instant invention, this desirable pH range can be approached down to a pH value of about 5. Dyebaths according to the invention should not be used below this pH value because the one-phase system would break down.

As component (a) of the mixed carrier in the dyebaths according to the invention, salts of suitable saturated aliphatic carboxylic acids are used, for example, alkali salts such as lithium, sodium or potassium salts, ammonium salts or N-alkylor N-hydroxyalkylammonium salts or alkoxy-alkyl-substituted ammonium salts of caprylic acid, pelargonic acid, capric acid, lauric acid or myristic acid, or of the acid mixtures all comprehended by the inclusive term coconut oil fatty acids, or of cyloxyacetic acid, lauryloxy acetic acid, decylthioacetic acid or laurylthioacetic acid. Examples of N-substituted ammonium salts of the acids mentioned are derived from primary, secondary or tertiary amines, e.g. from monoalkylamines such as methyl, ethyl, propyl or isopropyl amine, from hydroxyalkylamines such a S-hydroxyethyl, or por -hydroxypropyl amine, from dialkylamine such as diethylamine, and, in particular, from bis-(hydroxyalkyl)-amines such as bis-(,B-hydroxyethyD-amine or bis- -hydroxypropyD-amine or from bis-([i,y-dihydroxypropyl)-amine, from N-alkyl-N-(hydroxyalkyl)-amines such as N-methylor N-ethyl-N-(fl-hydroxyethyl)-amine or N-methylor N-ethyl-N-(' -hydroxypropyl)-amine, also from strong cyclic nitrogen bases such as morpholine, from trialkylamines, particularly from tri-(hydroxyalkyl)- amines, e.g. from tri-(,B-hydroxyethyl-amine), from N-alkyl-bis-N-(hydroxyalkyl)-amines such as N-methylor N-ethyl-N,N-bis-(B-hydroxyethyD-amine or N-methylor N-ethyl-N,N-bis-(,B- or 'y-hydroxypropyD-amine or N-ethyl-N,N-bis-(B,'y-dihydroxypropyl)-arnine, or from diamines, i.e. hydroxyalkylated diamines such as tetrahydroxyethyl-ethylenediamine. The alkali, alkylamonium or hydroxyalkylammonium salts, mainly the (B-hydroxyethyl)-ammonium salts, bis-(,B-hydroxyethyl)-ammonium salts, bis-('y-hydroxypropyl)-ammonium salts, methyl- (B-hydroxyethyl)-ammonium salts, methyl-bis (fi-hydroxyethyl)-ammonium salts or methyl-(fi,' -dihydroxypropyl)- ammonium salts of coconut oil fatty acids have proved to be particularly good.

As component (b) of the mixed carrier in the dyebaths according to the invention, namely reaction products of 4 to 12, preferably 5 to 10 equivalents of ethylene oxide with one equivalent of, e.g., octyldecyl-, dodecyl-, tetradecyl-alcohol or with one equivalent of one of the fatty acids mentioned above are used as polyglycol ethers.

The other auxiliaries mentioned under (b) which may be present in the impregnation liquors are essentially the following: inorganic salts such as sodium chloride or sodium sulfate, particularly as chromic acid salts when metallizable dyestuffs are used, also lower alkanoic acids such as acetic acid, but principally amides of saturated aliphatic monocarboxylic acid having 8 to 14 carbon atoms which are derived from primary and secondary amines having at least one low hydroxyalkyl group. When such amides are present in the liquor, the weight ratio of amides to mixture of the water-soluble salts and polyglycolethers must be about 1:2 or less. Suitable amides are derived, for example, from the higher fatty acids and mono-hydroxy-lower alkylamines described above, e.g. fi-hydroxyethylamine, -hydroxypropylamine or fi,'y-dihydroxypropylamine, bis-(hydroxy-lower alkyl)-amines such as bis-(fl-hydroxyethyl)-amine or bis-(y-hydroxypropyl)-amine or bis-(u-methyLfi-hydroxyethy1)-amine, N-alkyl-N-hydroxy-lower alkyl)-amines such as N-methylor N-ethyl-N-(B-hydroxyethyl)-amine or N-methylor N-ethyl-N-(-y-hydroxypropyl)-amine as well as the lower alkyl ethers, particularly the methyl or ethyl ethers, of the hydroxy-lower alkylamines mentioned such as fl-methoxyor fl-ethoxy-ethylamine or -methoxyor 'y-ethoxy-propylamine.

Lower as used in thi specification and the appended claims in connection with an aliphatic radical such as an alkyl, alkoxy or alkanoyl radical means a radical from 1 to 4 carbon atoms.

The acid wool dyestuffs usable according to the invention, i.e. those which are present as anions in a neutral to weakly acid dye bath, can be of any class of dyestuffs desired. For example, they can be metal-free, heavy-metal containing or metallizable monoor poly-azo dyestuifs, formazane, anthraquinone, phthalocyanine or nitro dyestuffs. The process according to the invention is suitable in particular for dyeing with metallizable azo dyestuffs, this in the presence of soluble chromic acid salts, or with meta1-containing azo dyestuffs, preferably with monoazo dyestuffs which contain 2 molecules of azo dyestuff bound to one heavy metal atom such as chromium or cobalt.

The thickeners used are the products known in textile printing, in particular the water soluble salts of alginic acids. However, also cellulose derivatives such as methyl cellulose or soluble salts of carboxymethyl cellulose can be used. Sufficient amounts of thickener should be used in the dye liquors according to the invention to impart to those liquors a viscosity of about 35 to 75 centipoises.

Both natural and also synthetic polyamide fibers can be dyed according to the invention. Examples of natural polyamides are wool and silk; examples of synthetic polyamides are nylon, Perlon (Perlon-Warenzeichenverband, registered company, Frankfunt am Main, Germany), Rilsan (Socit Organico, Paris, France) or Grilon (F. Emser Werke, Ems, Switzerland), etc. Sometimes a drying of the impregnated synthetic polyamides under thermo-fix conditions, i.e. for example. at a temperature of 250 is advantageous. The dyeing process according to the invention is employed chiefly for W001. This is finished under more mild conditions, e.g. in a hot to boiling acid bath or by steaming.

The polyamide material can be dyed according to the invention in any form desired, for example in the form of flakes, slubbing, yarn or fabrics, the latter two after the conventional chlorination prior to printing, or even Without such chlorination. Mixed fibers such as cellulose fibers mixed or encased with polyamides, particularly also in the form of mixed fabrics, can also be dyed, in particular mixed fabrics of wool and polyester fibers such as cellulose acetate, cellulose triacetate and, particularly, polyterephthalic acid diol ester fibers. Only the polyamide (wool) portion can be dyed or also the polyamide portion can be dyed according to the invention and the polyester portion can be dyed simultaneously with dispersion dyestuffs.

The fibers are impregnated by conventional techniques, e.g. by printing, coating or spraying, preferably however,

by padding (foularding). Impregnation solutions according to the invention are advantageously produced by mixing warm aqueous dyestutf solutions of suitable concentration which may contain thickeners with the desired amount of a mixture of fatty acid salts and polyglycol ether as defined, as well as, optionally, with one or several of the above-named further auxiliaries, The impregnation liquor preferably contains about to 60 g./liter of a soluble salt of saturated aliphatic monocarboxylic acid having 8 to 14 carbon atoms and 5 to 30 g./liter of a polyglycol ether of fatty alcohols or'fatty acids having 8 to 14 carbon atoms, which polygolycol ethers contain 4 to 12 ether groups and optionally other auxiliaries and preferably an amide of saturated, aliphatic monocarboxylic acids having 8 to 14 carbon atoms; the liquor has the above-mentioned pH range, or is adjusted to the same in the usual manner. The polyamide fibers are impregnated advantageously at 40-70 C. and then wrung out to the desired content of impregnation liquor which is about 40 to 110% of the weight of the fibers, and preferably at least 80% in the case of wool.

When the impregnated polyamide fibers are steamed this is done by the usual methods, advantageously with neutral saturated steam. Wool and silk are steamed at about 90-120 C.; synthetic fibers are steamed at 90- 140 C.; the preferred temperature range for steaming under substantially ambient pressure is at about 101 to 103 C.

The fixing of the dyestuif of the polyamide fibers by treatment in a hot acid bath is performed by the known methods. Advantageously the content of acid for this purpose is about 5 to 15 g./liter. The goods are introduced into the acid bath advantageously at 80-98 C. Inorganic and organic acids are suitable for the acid bath. Examples of suitable inorganic acids are sulfuric acid, phosphoric acid or hydrochloric acid and examples of suitable organic acids are formic acid or acetic acid. Organic aclds are preferred, in particular formic acid. In some cases it is useful to also add to the acid bath water-soluble salts, preferably water-soluble calcium salts of mineral acids, in particular calcium chloride.

The goods treated by acid shoe or by steaming are rinsed with cold or warm water which can contain the auxiliaries usual in the dyeing industry, e.g. formic acid or acetic acid, or also wetting or wash-active substances.

Compared with similar known processes, the process for the dyeing of polyamide fibers according to the mvention has the following advantages: the impregnation liquor is homogeneous and substantially insensitive to electrolytes, it is thus more stable in the continuous process; in addition, even when producing very deep shades, a more level dyeing is obtained; it is also possibleto dye blended wool material of various origin and quality and nevertheless obtain the same good level dyeings as with wool of a single source and quality, particularly when the dyebath contains the above-described amides of saturated aliphatic monocarboxylic acids as ad uvant besides the decisive homogenity-maintaining mixture of water-soluble salts (a) and polyglycolethers (b). The fibers dyed according to the invention retain a soft feel and can be spun better; also the impregnation liquors are easily produced, they have, so to speak, unlimited stability and they do not substantially soil the apparatus; finally, a previous drying of the impregnated goods can be avoided which is a saving in time and apparatus.

In a second aspect, this invention concerns a process for producing prints on woollen goods, particularly on non-chlorinated woollen woven fabrics and yarns, by fabric printing methods; it further relates to the printing pastes used for this purpose as well as, as industrial product, the woollen fabrics and yarns so printed.

It is known that sufficiently vivid woollen prints of the necessary color strength can only be attained on chlorinated woollen woven fabrics or yarns. This naturally necessitates a pre-treatment of the woollen goods to be printed with chlorine-containing liquor, especially aqueous sodium hypochlorite solution which, apart from the additional work involved, also has the disadvantage that it injures the wool fibers. Another disadvantage of the known process is that chlorinated woollen fabrics and yarn by fabric-printing methods, give only uneven and dull prints which in no way meet the present day requirements of the printing industry. Therefore, the printing of unchlorinated wool has only been applied in Vigoureux printing, usually of black and grey shades on woollen slubbing which is used, for instance, in the manufacture of fil-a-fil gents and ladies apparel in cases where dyed prints are not objectionable.

It is, therefore, an object of this aspect of the invention to provide a process which permits obtainment of strong prints on unchlorinated wool fabric, whereby the disadvantages connected with the known chlorination of the woollen fabrics and yarns prior to printing are avoided. The prints produced on unchlorinated Wool by this process according to the invention are just as good as those attained on chlorinated wool.

The process according to this aspect of the invention consists in printing unchlorinated woollen fabrics or yarns at room temperature and a pH of at least 2, with a printing paste which contains at least one acid wool dyestutf, which paste contains as carrier soluble salts of saturated, aliphatic monocarboxylic acids having 8 to 14 carbon atoms as well as polyglycol ethers of fatty alcohols or fatty acids having 8 to 14 carbon atoms, which polyglycol ethers have 4 to 12 other groups, and, optionally, other auxiliaries, and fixing the printed goods by steaming with subsequent rinsing.

By fabric printing as used in describing this aspect of the invention, there is meant only the textile printing of fabrics or yarn, and not the Vigoureux printing methods mentioned, hereinbefore.

The above-mentioned fixing treatment of the freshly printed-on woollen fabric or yarn involves drying the said material at a temperature not exceeding 70 C., preferably of about 40 to 60 C., and then steaming the material with saturated steam of about 101102 C. in a conventional steaming apparatus.

The steamed, printed material is then rinsed in cold water and may then either be allowed to dry or may be subjected to other conventional finishing treatments, such as soaping and the like.

As salts of saturated aliphatic carboxylic acids, the printing paste used according to the invention contains, for example, alkali metal salts such as lithium, sodium or potassium salts, or also ammonium salts of caprylic, pelargonic, capric, lauric or myristic acid or the salts of the mixture of acids comprised in the term coconut oil fatty acids, or of decyloxy, lauryloxy, decylmercapto or laurylmercapto acetic acid. In ammonium salts, the

ammonium ions can contain N-substituents, particularly alkyl groups having 1 to 4 carbon atoms which alkyl groups may be substituted by the hydroxyl group or by a lower alkoxy group, preferably of 1 to 2 carbon atoms.

Particularly, polyglycol ethers having 5 to 10 ether groups are useful in the fabric printing pastes according to the invention. These polyglycol ethers are the reaction products of fatty alcohols or fatty acids, having 8 to 14 carbon atoms, with from 5 to 10 equivalents of ethylene oxide: preferably, lauryl alcohol is used as fatty alcohol,

and as fatty acids there are used those mentioned above in the discussion of the carboxylic acid salts, in particular the coconut oil fatty acids.

Advantageously, the weight ratio of the fatty acid salts as defined to the polyglycol ethers in the paste is about 1:1.

Particularly beautiful prints are obtained with a printing paste which also contains amides obtained by reaction of saturated, aliphatic monocarboxylic acids having 8 to 14 carbon atoms with ammonia or primary or secondary amines which contain at least one hydroxy-lower alkyl group. Such amides are derived, for example, from the fatty acids mentioned above in the discussion of the salts of fatty acids and from ammonia or the following aliphatic amines:

(a) .Mono-(hydroxy-lower alkyl)-amines such as B-hydroxyethylamine, y-hydroxypropylamine or ;3,' -dihydroxypropylamine,

(b) Bis-(hydroxy-lower alkyl)-amines such as bis-(,8- hydroxyethyl)-amine, bis-(' -hydroxypropyl)-amine or bisa-methyl-fi-hydroxyethyl) -amine,

(c) N-alkyl-N-(hydroxy-lower alkyl)-amines such as N-methylor N-ethyl-N-(B-hydroxyethyD-amino, or N- methylor N-ethyl-N-(hydroxy-propyl)-amine.

The bis-(hydroxyalkyl)-amides of the fatty acids described above, particularly of the coconut oil fatty acids, are preferred, and especially those amides the hydroxyalkyl radicals of which have from 2 to 3 carbon atoms, because they give a particularly good color yield.

These amides are obtained by reacting esters of suitable fatty acids with lower alkanols, e.g. fatty acid methyl or ethyl ester, with the desired amine, the reaction being performed in the presence of sodium or potassium alcoholate.

The printing paste to be used according to this aspect of the invention contains, as carrier, the fatty acid salts and polyglycol ethers as defined under the first aspect of the invention, as well as, optionally, the amides mentioned above, preferably in amounts of, in all, about 20 to 40 grams, preferably in amounts of about 30 grams per kilogram of paste. In addition, it contains thickeners in amounts conventional in the fabric printing industry, in particular soluble types of gum such as so-called crystal-gum, or thickeners having a cellulose basis such as carob bean flour, tragacanth, galactomaunan, British gum, or-in alkaline 1nediumalso the watersoluble salts of alginic acids, or cellulose derivatives such as methyl cellulose or soluble salts of carboxymethyl cellulose. As further auxiliaries, the paste can also contain acids, in particular lower fatty acids such as formic acid and, mainly acetic acid, organic solvents such as alcohols, particularly lower alkanols such as isopropanol, glycols such as ethylene glycol or thiodiethylene glycol, or triols such as glycerin, as well as carbonic acid amides and thiocarbonic acid amides, in particular urea or thiourea.

The acid wool dyestuffs in the printing paste usable according to this aspect of the invention can be of the most various classes of dyestuffs. Preferably they are of the technically proved classes of azo, anthraquinone, phthalocyanine, nitro or formazane dyestuffs which, if desired, may also contain metals such as copper, nickel, chromium or cobalt. As azo dyestuffs, mainly monoazo dyestuffs are used, e.g. those of the type benzene-azohydroxybenzene, benzene-aZo-aminobenzene, benzeneazo-hydroxynaphthalene, benzene-azo-aminonaphthalene, benzene-azo-hydroxypyrazole, benzene azo-aminopyrazole, benzene-azo-acyloacetylarylamide or those of the analogous naphthalene-azoand heterocycle-azo types, Whereby as heterocycles, five or six-membered heterocycles, particularly those containing nitrogen, can be mentioned such as thiazoles, imidazoles, triazoles, oxdiazoles, thiadiazoles, pyrimidines, benzothiazoles, benzotriazoles, indazoles, quinolines. However, also polyazo dyestuffs can be used. The azo dyestuffs can be metallized, principally by chromium or cobalt, but also by copper or nickel. Particularly favorable results are produced by heavy-metal containing azo dyestuffs, i.e. chromium or cobalt containing azo dyestuffs, preferably monoazo-dyestuffs which contain one metal atom bound to two molecules of dyestuif.

The woollen fabrics and yarns to be printed according to this aspect of the invention can be of pure wool or mixed fabrics, in the latter case preferably a blended fabric of wool and polyester fibers. By polyester is meant high molecular organic esters such as cellulose dito tri-acetate, particularly, however, polymeric esters of aromatic polycarboxylic acids with polyvalent alcohols, especially polyglycol terephthalates. It is possible to print only the wool part or also both the wool and polyester parts together.

The woolen fabric or yarn is printed and the printed goods are steamed by conventional methods. Beautiful, strongly colored prints are obtained.

The printed goods are advantageously rinsed, for example, with cold or warm water which can contain the auxiliaries usual in textile printing, e.g. formic acid or acetic acid, or, wet-ting agents or detergents.

The following non-limitative examples serve to illustrate the invention further. The temperatures given therein are in degrees Centigrade. Where not otherwise stated, parts and percentages are given by weight. The relationship of parts by weight to parts by volume is as that of grams (g.) to milliliters (ml.). C.I. means Color Index, second edition, 1956, published by The Society of Dyers and Colourists, Bradford, England, and The American Association of Textile Chemists and Colorists, Lowell, Mass, U.S.A.

Example 1 40 parts of the commercial form of the chromium complex compound of the monoazo dyestuif 2-aminophenol-4-methylsulfone +1 phenyl-3-methyl-pyrazolone (molar ratio of dyestuifzchromium is 2:1)containing about of dextrin as diluting agent (coupage)--are dissolved in warm mixture of 300 parts of an aqueous 2.5%-solution of carob bean flour and 30' parts of a carrier mixture consisting of bis-(fi-hydroxyethyD-amine salt of coconut oil fatty acids and the condensation product of 1 mol of dodecyl alcohol and 5 mols of ethylene oxide in a weight ratio of 1:1, which 30 parts have been admixed with 250 parts of water. The resulting solution is diluted to 900 parts with warm water C.), and the pH is adjusted to about 6 with dilute acetic acid. The temperature of the mixture should then be about 60. Wool flannel is impregnated at 60 with this liquor, squeezed out to a liquor content of about calculated on the dry weight of the goods and steamed with saturated steam at 102 under slight excess pressure for 4 minutes. The goods are then washed with a solution containing 1 g./liter of nonylphenol polyglycol ether, then rinsed with water, then washed with an aqueous solution containing 2 mL/liter of %-formic acid and, if necessary, again rinsed with water. A level and well-penetrated orange wool dyeing is obtained which has no so-called sandwich effect.

If the steaming time in the above example is varied to 8, 15, 30 or 60 minutes, then in each case a weaker or deeper but otherwise equivalent orange wool dyeing is obtained.

By using, in the above example, instead of the dyestuif mentioned, similar chromium-containing monoazo dyestuffs of the type containing 2 dyestutf molecules per chromium atom (2:1 complexes) which contain no sulfonic acid groups but which are substituted by lower alkyl-sulfonyl groups or which contain sulfonic acid amide groups which may be substituted at the nitrogen atom by alkyl groups, for example, the chromiumcontaining dyestuff:

2-aminophenol 5 sulfonic acid amide l-phenyl-3- methyl-pyrazolone, the chromium-containing dyestuif mixture:

2 amino 5 nitrophenol- 2 hydroxynaphthalene,

2 amino-S-nitrophenol1-hydroxynaphthalene-3,6- bis sulfonic acid methylamide (dyestutfzchromium=2:l) or the chromium-containing monoazo dyestuif:

2 aminophenol 4 methylsulfone l-acetylamino-7- hydroxy-naphthalene (dyestutf chromium=2: 1),

while otherwise the procedure given in the above example is followed: equally well penetrated and level red, navy blue or grey colored wool flannel dyeings, respectively, are obtained.

By using, instead of the carrier mixture given in the above Example 1, the same amount of a mixture which consists of: 1 part of the sodium or potassium salt of coconut oil fatty acids and 1 part of the condensation product of 1 mol of decyl alcohol and 6 mols of ethylene oxide or 1 part of N-methyl-N-(fi-hydroxyethyD-amine salt of lauric or myristic acid and 1 part of the condensation product of 1 mol of tetradecyl alcohol and 6 mols of ethylene oxide, and otherwise following the procedure given in the example, paragraph one, equally well penetrated and level dyeings are obtained.

Similarly good results are obtained when using, in the above example, instead of carob bean flour solution, an identical amount of aqueous sodium alginate solution.

Example 2 W001 flannel is impregnated at 6 with an impregnation liquor produced according to Example 1, first paragraph, and wrung out to a liquor content of about 80%. The foularded fabric is passed through a 98 hot aqueous bath which contains 3 ml./liter of aqueous 85%- formic acid at a rate allowing the material to be in the bath for 5 minutes. Only a negligible bleeding of the dyestuff into the bath occurs. The wool flannel so dyed is then washed for 5 minutes with a 45 warm aqueous solution of 0.5 g./liter of nonylphenol polyglycol ether and then rinsed with cold water. The orange dyeing obtained i well penetrated and has no so-called sandwich effect.

By using, instead of the carrier mixture given in EX- ample 1, first paragraph, the same amount of a mixture consisitng of, in a weight ratio of 1:1, tri-(B-hydroxyethyl)-amine salts of coconut oil faty acids, bislB-hydroxyethyD-amine salts of coconut oil fatty acids, dimethylamine salts of coconut oil fatty acids, or the morpholine salt of coconut oil fatty acids or N-methyl- N,N-bis-(fl-hydroxyethyD-amine salt of coconut oil fatty acids, bis-(fi-hydroxyethyD-amine salt of lauric acid, bis- (B-hydroxyethyD-amine salt of pelargonic acid, ethylamine salt of coconut oil fatty acids or the sodium or potassium salt of coconut oil fatty acid with, in each case, the condensation product of 1 mol of dodecyl alcohol and 5 mols of ethylene oxide is used and otherwise the procedure described in the example is followed, then equally well penetrated and level dyeings are obtained.

Example 3 W001 flannel is impregnated in the foulard at 40 with a liquor which, instead of the metal-containing azo dyestuft mentiond in peragraph 1 of Example 1, contains the dyestuff Polar Brilliant Blue GAW (Cl. 61135, Acid Blue 127), but which is otherwise produced according to paragraph 1 of Example 1, and wrung out of a liquor content of 80%. The goods are then steamed for 4 minutes at 102 under slight excess pressure. The goods are then Washed with a solution containing 1 g./ litre of nonylphenol polyglycol ether, then rinsed with water, washed with an aqueous solution containing 2 ml./liter of 85% formic acid and, if necessary, again rinsed with water.

A level and well penetrated blue wool dyeing is obtained which has no so-called sandwich effect.

Instead of Polar Brilliant Blue GAW, the disazo dyestuif coupled in acid medium of the formula is used and otherwise the procedure described in the example is followed, then equally good and level red material which is well penetrated is obtained.

Example 4 40 parts of the disazo dyestuif are dissolved in a 60 warm mixture of 300 parts of a 2.5 aqueous sodium alginate solution and 30 parts of a mixture of, in a weight ratio of 1:1, bis-(B-hydroxyethyl)-amine salt of coconut oil fatty acid and the condensation product of 1 mol of dodecyl-alcohol and 10 mols of ethylene oxide, which 30 parts have been diluted with 250 parts of water. The solution obtained is diluted with warm water to 1000 parts. The temperature should be 60.

Woollen slubbing is impregnated at 60 with this solution, the pH of which has been adjusted to 6 with acetic acid, wrung out to a liquor content of about and steamed for 30 minutes at 98 under slight excess pressure. The goods are then rinsed with a 50 warm aqueous solution of 0.5 g./ litre of a condensation product according to US. Patent 2,089,212, then rinsed with water at about 30, then treated with a 30 warm aqueous solution of 0.2 ml./liter of a formic acid and finally rinsed again with 30 warm water.

Woollen slubbing which is evenly dyed red is obtained. It can be well combed and spun.

NHg

acid 1103s- Example 5 80 parts of Eriochrome Black A (CI. 15710) are dissolved in a 60 warm mixture of 300 parts of a 2.5% sodium alginate solution and 30 parts of a mixture consisting, in a weight ratio of 1:1, of N-methyl-N-(B-hydroxyethyl)-amine salt of coconut oil fatty acid and of the condensation product of 1 mol of coconut oil fatty acids and 5 mols of ethylene oxide, as well as 10 parts of potassium chromate, both said mixture and potassium chromate being dissolved in 250 parts of warm water. The solution obtained is diluted with water to 1000 parts; the temperature should be 20.

Woollen slubbing is impregnated with this liquor at 20-30, wrung out to a liquor content of about and steamed with saturated steam for 1 hour at 98. The goods are then rinsed with an aqueous solution of 0.5 g./liter of a condensation product according to US. Patent 2,089,212 in a back-washing machine, rinsed with water at about 30, then acidified in a new bath with an aqueous 30 warm solution of 0.2 ml./liter of 85% formic acid and finally again rinsed with 30 warm water.

Woollen slubbing dyed a level black is obtained. It can be well combed and spun.

Example 6 45 parts of Eriochrome Red B (C.I. 18,760), 27.5 parts of Eriochrome Brilliant Red BL(C.I. 17995) and 0.9 part of Eriochrome Blue SE (CI. 16680) are dissolved in a 60 warm mixture of 300 parts of a 2.5% aqeous sodium alignate solution and 30 parts of a mixture of, in a weight ratio of 1:1, N-methyl-N-(u-hydroxyethyl)amine salt of coconut oil fatty acid and the condensation product of 1 mol of tetradecyl alcohol and 7 mols of ethylene oxide, as well as 10 parts of sodium chromate, in mixture with 250 parts of warm water. The solution obtained is diluted with warm water to 1000 parts. The temperature should be 60.

Woollen slubbing is impregnated with this liquor at 60, wrung out to a liquor content of about 80% and steamed for 30 minutes at 98 with saturated steam. The

goods are then rinsed with a 50 warm aqueous solution of 0.5 g./liter of a condensation product according to U.S.P. 2,089,212, rinsed with water at about 30, then treated with a 30 warm aqueous solution of 0.2 ml./ liter of 85% formic acid and finally again rinsed with 30 warm Water.

Level, red, penetrated woollen slubbing is obtained which can be well combed and spun.

If in the above example instead of the dyestuffs given, a mixture is used consisting of 28 g./liter of Eriochrome Cyanine R (C.I. 42,571) and 0.9 g./liter of Eriochrome Blue SE (C.I. 16680) and otherwise the procedure given in the example is followed, then an equally well dyed and penetrated blue woollen slubbing dyeing is obtained.

Example 7 Silk serge is impregnated at 40 with an impregnation liquor produced according to Example 1 paragraph 1, wrung out to a liquor content of 80% and treated for minutes in a 98 warm aqueous bath which contains 8 ml./liter of 85 formic acid. Only a very slight bleeding of the dyestulf into the acid bath occurs. The goods are afterwards washed with a 45 warm aqueous solution of 0.5 g./liter of nonylphenol polyglycol ether and then rinsed with cold water.

In this way, Well penetrated orange silk serge of good evenness is obtained which has no so-called sandwich elfect.

Example 8 37.5 parts of the cromium-containing monoazo dyestiff: 2 carboxy-l-aminobenzene 1-phenyl-3-methylpyrazolone (dyestuifzchromium=2:1), and 14.0 parts of the chromium-containing monoazo dyestulf: Z-aminophenol- 4-sulphonic acid methylamide 1-carboethoxyamino-7-hydroxynaphthalene (dyestuif:chromium=2:1) are dissolved in an 80 warm mixture containing 300 parts of a 2.5% aqueous sodium alginate solution and parts of a mixture, in a weight ratio of 1:1, of N-methyl-N-(B-hydroxyethyl)-amine salt of coconut oil fatty acid with the condensation product of 1 mol of dodecyl alcohol and 7 mols of ethylene oxide, which 10 parts are admixed with 290 parts of water, and the solution obtained is diluted with cold water to 1000 parts. The temperature is then about 40.

Nylon canvas is impregnated with this liquor, wrung out to a liquor content of 50% of the weight of the fibers, steamed for 8 minutes at a temperature of 130 and then rinsed first with hot and then with cold water.

An olive, well penetrated nylon canvas is obtained and the dyeing is very level.

Example 9 Nylon canvas is impregnated at 40 with an impregnation liquor produced according to Example 8, paragraph 1 but which only contains /3 of the amount of dyestuff given in that example. The goods are then wrung out to a liquor content of 50% of the weight of the fibres and then treated for 4 minutes in a 98 warm aqueous bath containing 4 ml./liter of 85 formic acid. Only an inconsiderable bleeding of the dyestutf into the acid bath occurs. The nylon canvas so dyed is then rinsed with warm and cold water; a good and level olive dyeing is obtained.

Example 10 A poly e aminocaprolactam (Perlon, Perlon-Warehzeichenverband, registered company, Frankfurt am main, Germany) is impregnated at 40 with a liquor produced according to Example 9, wrung out to a liquor content of 50% of the weight of the fibres and dried under thermofix conditions for 45 seconds at 190.

The Perlon canvas so impregnated is entered into a 98 warm aqueous bath which contains 4 ml./liter of 85% formic acid and treated in this bath for 4 minutes at the boil. It is then rinsed first with warm and then with cold water.

An evenly penetrated olive Perlon canvas is obtained.

Example 11 2.5 parts of the cobalt-containing monoazo dyestuff: 2- aminophenol-4-sulphonic acid methylamide l-phenyl-3- methylpyrazolone (dyestuff:cobalt=2:1) and 0.5 part of the chromium-containing monoazo dyestuff: 2-amino-4- nitrophenol 1 phenyl 3-methyl-pyrazolone (dyestuif: chromium=2:1) are dissolved in an warm mixture of 300 parts of a 2.5% aqueous sodium alginate solution and 30 parts of a mixture of, in a weight ratio of 1:1, N-methyl-N-(li-hydroxyethyl)-amine salt of coconut oil fatty acid with the condensation product of 1 mol of dodecyl alcohol and 5 mols of ethylene oxide. The solution obtained is diluted with sufiicient cold water to make 1000 parts by volume. Woollen slubbing is impregnated at 40 with this liquor, the pH of which has been adjusted to 6 by the addition of acetic acid, wrung out to a liquor content of 103% calculated on the fibres, and then steamed for 8 /2 minutes at 104 with saturated steam.

The goods are then washed with a solution containing 1 g./litre of nonyl phenol polyglycol ether and 1 ml./ liter, of concentrated ammonia solution, then rinsed with water, then washed with an aqueous solution containing 2 mL/Iiter of formic acid and, if necessary, again rinsed with water.

The orange-red woollen slubbing so dyed is well penetrated and is very level. The feel of the goods is soft and voluminous and the material can be well combed and spun.

Example 12 Woollen slubbing is printed in the known manner of Vigoureux printing with a solution produced according to Example 1, paragraph 1 but which contains 500 parts instead of 300 parts of sodium alginate solution and instead of the dyestuff given in that example, 40 parts of the chromium-containing monoazo dyestutf Z-aminophenol-4-sulfonic acid ethylamide 1-acetylamino-7-hydroxynaphthalene (dyestuff:chromium=2:l). The take-up of liquor is about 60%.

The goods are after-treated by steaming and rinsing as described in Example 1.

Grey coloured woollen slubbing is obtained which is distinguished by a full voluminous feel. The goods can be combed and spun well.

Example 13 40 parts of the chromium-containing monoazo dyestuff 2 aminophenol-4-methylsulfone 1-acetylamino-7- hydroxynaphthalene (dyestutf:chromium=2:1) are dissolved in a 60 warm mixture of 300 parts of a 2.5% aqueous sodium alginate solution and 15 parts of N- methyl-N-(fl-hydroxyethyD-amine salt of coconut oil fatty acid, 15 parts of the condensation product of 1 mol of tetradecyl alcohol and and 6 mols of ethylene oxide, and 15 parts of coconut fatty acid N,N-bis-(fi-hydroxyethyl)- amide, mixed with 250 parts of water. The solution obtained is made up to 1000 parts with water. The temperature of the solution should be 60.

Wool flannel is impregnated at 60 with this liquor, and wrung out to a liquor content of 80%. The foularded fabric is entered into a 98 warm aqueous bath which contains 8 ml./liter of 85% formic acid and is treated in this bath for 5 minutes.

The grey wool flannel dyed in this way is washed with a 45 warm aqueous solution of 0.5/liter of nonylphenol polyglycol ether and then rinsed with cold water. In this way a well penetrated grey wool flannel is obtained which has good evenness and is without a so-called sandwich effect.

If in the above example instead of the dyestuff mentioned the cobalt-containing monoazo dyestuff 2-amino- 4 chlorophenol 2-hydroxynaphthalene-6-sulphonic acid methylamide (dyestuff:cobalt=2:l) or the chromium- 13 containing monoazo dyestulf 2-amino-4-chlorophenol 1- hydroxynaphthalene-3-sulphonic acid amide (dyestutf: chromium=2:1) is used and otherwise the procedure given in the example is followed, then Wool flannel dyed ruby red or blue respectively is obtained. The dyeings are equally level and well penetrated.

Similarly good dyeings are obtained if, instead of the N-methyl-N-([3-hydroxycthyl)-amine salt mentioned in the example, the methylamine salt, morpholine salt, tri-(flhydroxyethyl)-amine salt, bis-(u-methyl-fl-hydroxyethyl) amine salt, sodium salt or potassium salt of coconut oil fatty acid or the fi-hydroxyethylamine salt of lauric acid is used in each case with the condensation product mentioned in the example.

Example 14 Woollen slubbing is foularded at 60 with an impregnation liquor produced according to paragraph 1 of Example 13 but containing the dyestulf Polar Brilliant Blue GAW (Cl. 61,135, Acid Blue 127) instead of the metalcontaining azo dyestuff mentioned in paragraph 1 of Example 13, and then wrung out to a liquor content of about 80%. The goods are then entered into a 98 warm aqueous bath containing 8 ml./liter of 85% formic acid. The goods are treated in this bath for 5 minutes.

Only an inconsiderable bleeding of the dyestuff into the acid bath occurs. The goods are then washed in a back-washing machine with a 50 warm aqueous solution of 0.5 g./litre of nonylphenol polyglycol ether, rinsed with water at 30, treated in a new bath with an aqueous solution of 1.5 ml./liter of 85% formic acid and then rinsed with 30 Warm Water.

The blue woollen slubbing so dyed is well penetrated and can be well combed and spun.

If instead of Polar Brilliant Blue GAW the dyestuffs mentioned in Example 3 paragraph 3 are used, then equally good and evenly penetrated woollen slubbing dyed red or yellow is obtained.

Example 15 Woollen worsted fabric is impregnated at 60 with an impregnation liquor produced according to Example 6 fourth paragraph and the goods are wrung out to a liquor content of 80%. The foularded fabric is then entered into a 98 warm aqueous bath containing 8 ml./liter of 85% formic acid. The fabric is treated in this bath for 5 minutes. An insignificant bleeding of the dyestuff into the acid bath occurs. The goods are then washed with a 45 warm aqueous solution of 0.5 g./ litre of nonylphenol polyglycol ether and then rinsed with cold water.

The woollen worsted so obtained is well penetrated and the blue dyeings are very level without any so-called sandwich effect.

Example 16 40 parts of the dyestuff Eriochrome Blue SE (C.I. 16,680) are dissolved in a 60 warm mixture of 300 parts of a 2.5% aqueous sodium alginate solution, to which are added 15 parts of N-methyl-N-(fi-hydroxyethyl)-amine salt of coconut oil fatty acid and 15 parts of the condensation product of 1 mol of dodecyl alcohol and 5 mols of ethylene oxide as well as 10 parts of potassium chro mate in 250 parts of water. The solution obtained is made up to 1000 parts With water and the pH is adjusted to 6 with acetic acid. The temperature should be 60.

Wool flannel is impregnated with this liquor at 60 and wrung out to a liquor content of 80%. The foularded fabric is entered into a 98 warm aqueous bath which contains 8 ml./liter of 85% formic acid and treated in this bath for 5 minutes. Only an inconsiderable bleeding of the dyestuff into the acid bath occurs. The blue wool flannel so dyed is then washed with a 45 warm aqueous solution of 0.5 g./litre of nonylphenol polyglycol ether and then rinsed with cold water. In this way a well penetrated very even blue wool flannel is obtained which has no so-called sandwich effect.

14 If in the above example instead of the dyestuff mentioned, Eriochrome Yellow G (Cl. 25,100) or Eriochrome Red G (Cl. 18,750) is used then corresponding yellow or red coloured wool flannel is obtained. The dyeing has equally good penetration and evenness.

Example 17 Wool flannel is impregnated and steamed according to Example 1. The goods, while still moist, are entered into a 98 Warm aqueous bath which contains 8 mL/liter of formic acid and are kept in this bath for 5 minutes, only an inconsiderable bleeding of the dyestuff occurring. The wool flannel so dyed is then washed in a 45 warm aqueous solution of 0.5 g./ liter of nonylphenol polyglycol ether and afterwards rinsed with cold water.

Well penetrated, very level orange wool flannel is obtained which has no sandwich effect.

Example 18 A fabric consisting of 45 parts of wool and 55 parts of Terylene (I.C.I., Manchester, England) is impregnated and steamed analogously to Example 1. The wool portion of the fabric is dyed orange whilst the polyester portion remains substantially undyed.

Example 19 A mixed fabric of wool and cellulose triacetate is impregnated and steamed analogously to Example 1. The wool part of the fabric is dyed orange whilst the triacetate part remains substantially undyed.

Example 20 Wool flannel is impregnated in the foulard at 40 with a liquor which, instead of the metal-containing azo dyestuff mentioned in paragraph 1 of Example 1, contains the dyestuff Polar Brilliant Red B (CI. 17995, Acid Red 133), but which is otherwise produced according to paragraph 1 of Example 1, and wrung out to a liquor content of 100%. The goods are then steamed for 15 minutes at about to 98 C. The goods are then washed with a solution containing 1 g./liter of nonylphenol polyglycol ether, then rinsed with water, washed with an aqueous solution containing 2 mL/liter of 85 formic acid and, if necessary, again rinsed with water.

A level and well penetrated red wool dyeing is obtained which has no so-called sandwic effect.

If, instead of Polar Brilliant Red B, the dyestuif coupled in acid medium of the formula is used and otherwise the procedure described in the example is followed, then equally good and level red material which is well penetrated is obtained.

Example 21 Woolen slubbing is foularded at 60 with an impregnation liquor produced according to paragraph 1 of Example 13 but containing the dyestuff Polar Brilliant Red B (CI. 17995, Acid Red 133) instead of the metalcontaining azo dyestufi mentioned in paragraph 1 of Example 13, and then wrung out to a liquor content -of about 100%. The goods are then entered into a 98 warm aqueous bath containing 8 ml./liter of 85 formic acid. The goods are treated in this bath for 5 minutes.

Only a momentary bleeding of the dyestuif into the acid bath occurs and this ceases immediately. The goods are then washed in a back-washing machine with a 50 Warm aqueous solution of 0.5 g./ liter of nonylphenol polyglycol ether, rinsed with water at 30, treated in a new bath 15 with an aqueous solution of 1.5 ml./liter of 85% formic acid and then rinsed with 30 warm water.

The red woolen slubbing so dyed is well penetrated and can be well combed and spun.

If, instead of Polar Brilliant Red B, the dyestuffs mentioned in Example 8, paragraph 3 are used, then equally good and evenly penetrated woolen slubbing dyed red or yellow is obtained.

Example 22 16 and 30 parts of lauric acid-N,N-bis-(/3-hydroxyethyl)- amide;

(d) 1 part of bis-(B-hydroxyethyl)-amine salt of coconut oil fatty acids, and 1 part of the condensation product of 1 mol of dodecyl alcohol and 5 mols of ethylene oxide;

(e) 1 part of the sodium salt of coconut oil fatty acids, and 1 part of the condensation product of 1 mol of decyl alcohol and 6 mols of ethylene oxide;

(f) 1 part of N-methyl-N-(fi-hydroxyethyl)-amine salt of lauric or myristic acid, and 1 part of the condensation 20 g. of the dyestuif C.I. Acid 85 (No. 22245) are mixed product of 1 mol of tetradecyl alcohol and 6 mols of with 60 g. of urea and the mixture is pasted with 50 ml. ethylene oxide; of cold water. 330 ml. of boiling water are poured over (g) 35 parts of N-methyl-N,N-bis-(fl -dihydroxyprothe paste and 50 g. of thidiethylene glycol, 400 g. of pyl)-amine salt of coconut oil fatty acid, 35 parts of aqueous 80%-acetic acid and 30 g. of myristyl alcohol pentaglycol ether and 30 parts of N,N-

(a) a mixture of 35 parts of the N-methyl-N,N-bisbis-(fl-hydroxyethyl)-amide of coconut oil fatty acid; (fl-hydroxyethyl)-aminesalt of coconut oil fatty acids, 35 (h) 35 parts of tri-(fl-hydroxyethyl)-amine salt of coparts of lauryl alcohol pentaglycol ether and 30 parts conut oil fatty acids, 35 parts of lauryl alcohol pentaglycol of N,N-bis-(;8-hydroxyethyl)-amide of coconut oil fatty ether and 30 parts of N,N-bis-(fi-hydroxyethyl)-amide of acid are admixed therewith in a conventional blender. coconut oil fatty acid;

The mixture is made up to 1000 g. with water. (i) 35 parts of dimethylamine salt of coconut oil fatty Closely woven Woolen fabric is printed by a convenacids, 35 parts of lauryl alcohol pentaglycol ether and tional fabric printing method with the above paste, dried 30 parts of N,N-bis-(fl-hydroxyethyl)-amide of coconut in a drying chamber at about 50, and then steamed with oil fatty acid; saturated steam of 101-102 and rinsed with cold Water. (j) 35 parts of morpholine salt of coconut oil fatty Vivid, brilliant, scarlet prints are obtained. acids, 35 parts of lauryl alcohol pentaglycol either and Prints having similar properties are obtained if, with parts of myristic acid-N,N-bis-(fl-hydroxyethyl)amide; otherwise the same procedure, instead of the 30 g. of (k) parts of ethylamine salt of coconut oil fatty the mixture (a) of amine salt, polyglycol ether and amide acids, 35 parts of lauryl alcohol pentaglycol ether and given in the example, the same amounts of the following 30 30 parts of N,N-bis-(fi-hydroxyethyl)-amide of coconut mixtures are used: oil fatty acid.

(b) 35 parts of bis-(fi-hydroxyethylamine) salt of If in the above example, with otherwise the same prococonut oil fatty acids, 30 parts of lauryl alcohol pentacedure, instead of the dyestulf mentioned in the example, glycol ether, and 30 parts of N,N-bis-('y-hydroxypropyL)- the same amounts of the dyestuffs given in column II amid of coconut oil fatty acid; 35 of the following Table I are used, then prints having simi- (c) 40 parts of the sodium or potassium salt of coconut lar properties are obtained which are of the shades given oil fatty acids, 35 parts of lauryl alcohol-decaglycol ether, in column III of the table.

TABLE I I II III Number Dyestuft Shade on wool 23 Green.

SOQNHQ E1. SO:

24 2-amino-4-uitrophenol+4-methylphenol (2:1 chromium complex) Brown' 25 NHz HzN Yellow.

1-phenyl-B-methyl-S-aminopyrazole4-sulphonic acid.

26. Mixture, consisting oi- Black.

parts of l-aminouaphthalene-5-su1phonie acid- 1-aminonaphthalene-d-phenylaminonaphthalene-S-sulphonic acid,

6 parts of 0.1. Acid Green 9 (No. 42100),

3.38 parts of Cl. Acid Orange 63 (N 0. 22870), reduced with 15.62 parts of sodium sulphate.

We claim:

1. Dye carrier composition consisting essentially of (a) a water-soluble salt of a saturated aliphatic monocarboxylic fatty acid having 8 to 14 carbon atoms with a monoto divalent cation selected from the group consisting of alkali metal ion, ammonium ion, lower alkyl-substituted ammonium ion, hydroxy-lower alkyl-substituted ammonium ion, lower alkoxy-alkyl-substituted ammonium ion, morpholinium ion, piperidinium ion, and hydroxy-(lower alkyl)-substituted ethylene-diammonium ion, and

(b) a polyglycolether selected from the group consisting of fatty alcohols and fatty acids having 8 to 14 carbons atoms, each mol of which is condensed with 4 to 12 equivalents of ethylene oxide, the weight ratio of (a) to (b) ranging from about 12:1 to 1.3.

2. Dye carrier composition consisting essentially of (a) one part by weight of bis-(fl-hydroxy-ethyl)-amine salt of coconut oil fatty acid and (b) one part by weight of the condensation product of dodecyl alcohol and ethylene oxide, in a molar ratio of 1:5.

3. Dye carrier composition consisting essentially of (a) one part by weight of N-methyl-N,N-bis-(hydroxyethyl)-amine salt of coconut oil fatty acid and (b) one part by weight of the condensation product of dodecyl alcohol and ethylene oxide, in a molar ratio of 1:5.

4. Dye carrier composition consisting essentially of (a) a water-soluble salt of a saturated aliphatic monocarboxylic fatty acid having 8 to 14 carbon atoms with a monoto divalent cation selected from the group consisting of alkali metal ion, ammonium ion, lower alkyl-substituted ammonium ion, hydroxy-lower alkyl-substituted ammonium ion, lower alkoxylower alkyl-substituted ammonium ion, morpholinium ion, piperidinium ion, and hydroxy-(lower alkyl)-substituted ethylenediammonium ion, and

(b) a polyglycolether selected from the group consisting of fatty alcohols and fatty acids having 8 to 14 carbon atoms, each mole of which is condensed with 4 to 12 equivalents of ethylene oxide, and

(c) an amide of a saturated aliphatic mono-carboxylic acid having from 8 to 14 carbon atoms and a member selected from the group consisting of monoand di-hydroxy-lower alkyl-amines and lower alkyl ethers thereof, the weight ratio of (a) to (b) ranging from about 12:1 to 1:3, and the weight ratio to the mixture of (a) and (b) being not greater than about 1:2.

5. Dye carrier composition consisting essentially of (a) a water-soluble salt of a saturated aliphatic monocarboxylic fatty acid having 8 to 14 carbon atoms with a monoto divalent cation selected from the group consisting of alkali metal ion, ammonium ion, lower alkyl-substituted ammonium ion, hydroxylower alkyl-substituted ammonium ion, lower alkoxylower alkyl-substituted ammonium ion, morpholinium ion, piperidinium ion, and hydroxy-(lower alkyl)-substituted ethylenediammonium ion, and

(b) a polyglycolether selected from the group consisting of fatty alcohols and fatty acids having 8 to 14 carbon atoms, each mol of which is condensed with 4 to 12 equivalents of ethylene oxide, and

(c) an amide of a saturated aliphatic mono-carboxylic acid having from 8 to 14 carbon atoms and a member selected from the group consisting of monoand dihydroxy-lower alkyl-amines and lower alkyl ethers thereof, the amount of (c) present being from 0 to a weight ratio of (c) to mixture of (a) and (b) of not greater than about 1:2, and the weight ratio of (a) to (b) ranging from about 12:1 to 1:3.

6. Dye carrier composition consisting essentially of (a) one part by weight of N-methyl-N-( 8-hydroxyethyl)-amine salt of coconut oil fatty acid,

(b) one part by weight of the condensation product of tetradecyl alcohol and ethylene oxide in a molar ratio 1:6, and

(0) one part by weight of coconut oil fatty acid-N,N-

bis-(B-hydroxy-ethyU-amide.

7. Dye carrier composition consisting essentially of (a) 35 parts by weight of the N-methyl-N,N-bis-(,B-hydroxyethyl)-amine salt of coconut oil fatty acids,

(b) 35 parts by weight of lauryl alcohol pentaglycol ether, and

(c) 30 parts by weight of N,N-bis-(,B-hydroxyethyl)- amide of coconut oil fatty acids.

References Cited UNITED STATES PATENTS 2,089,212 8/ 1937 Kritchvsky.

3,097,039 7/ 1963 Buehler et al 884 X 3,098,690 7/1963 Guion 8--84 X 3,188,291 6/1965 Hugues et al 252-117 X 3,203,900 8/1965 Carroll et al. 252110 FOREIGN PATENTS 1,117,437 5/1956 France.

903,781 8/ 1962 Great Britain.

OTHER REFERENCES R. Ca-sty: Melliand, 41, 11(1960), pp. 1365-1376. A. M. Schwartz et al.: Surface Active Agents, pp. 212- O 213, 1949, Interscience Publ., Inc., New York.

NORMAN G. TORCHIN, Primary Examiner T. J. HERBERT, JR., Assistant Examiner US. Cl. X.R. 

